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Elemental Analysis of Organic Species with Electron Ionization High-Resolution Mass Spectrometry

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Department of Chemistry and Biochemistry (UCB 215), Cooperative Institute for Research in the Environmental Sciences (CIRES, 216 UCB), and Department of Atmospheric and Oceanic Sciences (311 UCB), University of Colorado, Boulder, Colorado 80309
Cite this: Anal. Chem. 2007, 79, 21, 8350–8358
Publication Date (Web):October 4, 2007
Copyright © 2007 American Chemical Society

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    We present a new elemental analysis (EA) technique for organic species (CHNO) that allows fast on-line analysis (10 s) and reduces the required sample size to ∼1 ng, ∼6 orders of magnitude less than standard techniques. The composition of the analyzed samples is approximated by the average elemental composition of the ions from high-resolution electron ionization (EI) mass spectra. EA of organic species can be performed on organic/inorganic mixtures. Elemental ratios for the total organic mass, such as oxygen/carbon (O/C), hydrogen/carbon (H/C), and nitrogen/carbon (N/C), in addition to the organic mass to organic carbon ratio (OM/OC), can be determined. As deviations between the molecular and the ionic composition can appear due to chemical influences on the ion fragmentation processes, the method was evaluated and calibrated using spectra from 20 compounds from the NIST database and from 35 laboratory standards sampled with the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The analysis of AMS (NIST) spectra indicates that quantification of O/C is possible with an error (average absolute value of the relative error) of 30% (17%) for individual species. Precision is much better than accuracy at ±5% in the absence of air for AMS data. AMS OM/OC has an average error of 5%. Additional calibration is recommended for types of species very different from those analyzed here. EA was applied to organic mixtures and ambient aerosols (sampled at 20 s from aircraft). The technique is also applicable to other EI-HRMS measurements such as direct injection MS.

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     Department of Chemistry and Biochemistry.

     Cooperative Institute for Research in the Environmental Sciences (CIRES).


     Department of Atmospheric and Oceanic Science.


     Author to whom correspondence should be addressed. E-mail:  [email protected].

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